Block copolymers, synthesis and application as dehydrating and desalting of heavy crudes

ABSTRACT

The present invention is related to formulations consisting by block copolymers α,ω-di-aryl or alkyl sulfonates of poly(ethylene oxide) w -poly(propylene oxide)-poly(ethylene oxide) w  of bis-ammonium and block copolymers α,ω-di-amine of poly(ethylene oxide) w -poly(propylene oxide)-poly(ethylene oxide) w , that are effective in the dewatering and desalting crude whose specific gravities are within the range of 14 to 23° API.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims the benefit and priority to Mexican applicationNo. MX/a/2013/002243 with a filing date of Feb. 26, 2013, the disclosureof which is incorporated herein by reference in its entirely.

FIELD OF THE INVENTION

This invention is related with the synthesis of basic chemicals to breakup several kinds of water-oil emulsions and decrease its salt content.The invention is further directed to the synthesis of new copolymersblock α,ω-bifunctionalized with tertiary amines (aliphatic and aromatic)and their individual application and formulation as dehydrating anddesalting agents in crude oils with 14-23° API.

BACKGROUND OF THE INVENTION

The extraction of crude oil from reservoirs involves formation of waterin crude oil emulsions, crude oil in water emulsions and tertiaryemulsions water/crude oil/water and crude oil/water/crude oil. Suchemulsions are produced by the turbulence promoted by the pumping powerused in wells. These emulsions can be very stable and their formation isfavored and stabilized by compounds naturally present in crude oil suchas clays, naphthenic acids, rusty hydrocarbon and asphaltene. The wateremulsified in crude oil contains inorganic salts; mostly sodium,magnesium, calcium chlorides, carbonates and sulfates; and iron sulfidesand oxides. If not removed, these salts may cause various problems ofcorrosion and scaling in all the subsequent refining process (piping,storage tanks, distillation columns, heat exchangers, catalysts, pipingsystems, etc.). Additionally, the produced crude oil must comply withinternational quality standards relating to the maximum content of saltand water, for possible export [1].

Therefore, from an economic point of view, it is imperative andimportant to separate water from crude oil and simultaneously reduce thesalt content.

Since the last century, different chemical products have been used tocarry out the demulsification process of water in crude oil. The wateris commonly added as formulations consisting of groundbreaking agents,coalescing and emulsion clarifiers. The nature of these products arepolymeric.

Examples of polymeric formulations include alkoxylated alkylphenolresins formaldehyde [2], alkoxylated epoxy resins [2], block copolymersof polyoxyethylene-polyoxypropylene-polyoxyethylene (POE-POP-POE) andpolyoxypropylene-polyoxyethylene-polyoxypropylene (POP-POE-POP), usingvarious initiators such as propylene glycol or ethylenediamine [3],polyethers, polyesters and/or polyurethanes, polyesters together bydicarboxylic acids and/or diisocyanates [4], aliphatic and aromaticanhydrides in combination with glycolic esterified resins [5], ethylcellulose on nano magnetic particles crosslinked in combination with theapplication of external magnetic fields [6], cationic surfactants [7],symmetric type surfactants with polyoxyethylene spacers fragments [8]among some others.

The Mexican Petroleum Institute (Research Program in MolecularEngineering) proposed innovative solutions to the problem of dehydratingand desalting of crude oils, resulting in four patent applications inthis specific area. The formulations used triblock type copolymerspoly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) whichwere bifunctionalized with amines to dehydrate heavy crude oils,achieving water removal 30 to 80% and salts of heavy crude oils 30-65%[9-10]. Another method uses ionic liquids individually and formulationsfor dehydrating and desalting medium, heavy and extra heavy crude oils(API gravities between 8 and 20) where dehydrating and desaltingefficiencies reached about 90% and 76%, 90% and 71%, 90% and 71%,respectively. The addition of additives was done in concentrationsbetween 50 and 2000 ppm [11]. Another method involves the application ofsynergistic formulations of ionic liquids (IL's) and formulations oftriblock copolymers (CF's) α,ω-bifunctionalized with amines of ethylenepolyoxide-propylene polyoxide-ethylene polyoxide, each individually orin formulation, in crude oils whose gravities are between 9 and 30° API[12].

REFERENCES

-   [1] Atta A M, Abdel Rahman A A H, Elsaeed S M, AbouElfotouh S, Hamad    N A. Demulsification of crude oil emulsions using some new    water-soluble Schiff base surfactants blends. J. Disp. Sci. Technol.    2008; 29: 1484-1495.-   [2] Hellberg P E, Uneback I. Environmentally-friendly oil/water    demulsifier. Patent WO 2007/115980.-   [3] Abdel-Azim A A A, Zaki N N, Maysour, N E S. Polyoxyalkylenated    amines for breaking water-in-oil emulsions: Effect of structural    variations on the demulsification efficiency. Polymer. Adv. Technol.    1998; 9: 159-166.-   [4] Newman S P, Hahn C and McClain R D Environmentally friendly    demulsifiers for crude oil emulsions. US 2009/0259004.-   [5] Williams D E. Anhydride demulsifier formulations for resolving    emulsion of water and oil. US 2009/0306232.-   [6] Peng J X, Liu Q X, Xu Z H, Masliyah J. Novel magnetic    demulsifier for water removal from diluted bitumen emulsion. Energy    Fuels 2012; 26:2705-2710.-   [7] Mirvakili A, Rahimpour M R, Jahanmiri A. Effect of a cationic    surfactant as a chemical destabilization of crude oil based    emulsions and asphaltene stabilized. J. Chem. Eng. Data 2012;    57:1689-1699.-   [8] Feng J, Liu X P, Zhang L, Zhao S, Yu J Y. Dilational    viscoelasticity of the zwitterionic Gemini surfactants with    polyoxyethylene spacers at the interfaces. J. Disp. Sci. Technol.    2011; 32:1537-1546.-   [9] Cendejas G, Flores E A, Castro L V, Estrada A, Lozada M, Vázquez    F S (2008) Formulaciones desemulsificantes y deshidratantes para    crudos pesados a base de copolímeros en bloques bifuncionalizados    con aminas, Mx/a/2008/015756.-   [10] Cendejas G, Flores E A, Castro L V, Estrada A, Lozada M,    Vazquez F S (2010) Demulsifying and dehydrating formulations for    heavy crude oils base on block copolymers bifunctionalized with    amines, US 2010/0140141 A1-   [11] Flores E A, Castro L V, López A, Hernández J G, Alvarez F,    Vázquez F S, Estrada A, Lozada M. Deshidratación y desalado de    crudos medios, pesados y extrapesados utilizando líquidos iónicos y    sus formulaciones. Solicitud de patente mexicana (IMP-959,    MX/a/2011/003848).-   [12] Flores E A, Castro L V, López A, Hernández J G, Alvarez F,    Estrada A, Vázquez F S, Formulaciones sinérgicas de copolímeros    funcionalizados y líquidos ionicos para el deshidratado y desalado    de aceites crudos medianos, pesados y extrapesados. (IMP-953,    Mx/a/2011/004120).

These documents are hereby incorporated by reference in their entirety.

SUMMARY OF THE INVENTION

In the present invention, new compounds are synthesized as demulsifiersfrom block copolymers of poly(ethylene oxide)-poly(propyleneoxide)-poly(ethylene oxide) which are α,ω-bifunctionalized with tertiaryamines (aliphatic and aromatic). The compounds are evaluatedindividually in the dehydrating of different types of crude oils orblends, achieving efficiencies of dehydrating or desalting (78-100%) and(65-91%), respectively which outperforms the prior processes.

The present invention is also directed to a method of dewatering,desalting and breaking emulsions in crude oil and particularly heavycrude oil of 14-23° API. The method comprises the steps of adding aneffective amount of one or more α,ω-bifunctionalized poly(ethyleneoxide)-poly(propylene oxide)-poly(ethylene oxide) copolymer that isfunctionalized with aliphatic or aromatic tertiary amines. The triblockcopolymers have a polydispersibility of 1.02 to 1.20 and have amolecular weight of 1000 to 4000 Daltons. The copolymers are added in anamount of about 200 to 2000 ppm based on the amount of the crude oil. Inother embodiments, the copolymer can be used in amounts of about 150 to15000 ppm, and preferably about 200 to 1000.

The present invention is also directed to desalting and dewateringagents and formulations of the block copolymers in solvents or carriers.The formulations are then added to and mixed with the crude oil in anamount of provide an effective amount of the copolymers to dehydrate anddesalinate the crude oil. The formulations can contain one of the blockcopolymers or mixtures of two or more of the block copolymers.

The process of making the copolymer basically reacts an α,ω-dialkyl orα,ω-diaryl-sulfonate ester of poly(ethylene oxide)-poly(propyleneoxide)-poly(ethylene oxide) with an aliphatic or tertiary amine. Thepolyalkylene oxide typically has a molecular weight of about 1200-4500g/mol and a polydispersibility of 1.11-1.15.

The method of demulsifying, dehydrating and desalination of crude can beby mixing a composition or formulation with heavy crude oil. Thecomposition or formulation can be added in an amount of about 0.01% toabout 5% by weight to provide a concentration of about 100 to 6000 ppmof the total amount of the copolymers based on the amount of crude oil.The formulation can comprise a mixture of two or more of the copolymers.Mixtures of the copolymers can be added where each is included inamounts of about 100 to 300 ppm, and preferably about 200 to 300 ppmbased on the amount of crude oil.

In one embodiment of the invention, a combination of at least two of thecopolymers is mixed with crude oil. It has been found that a combinationof two copolymers provide a synergistic effect compared to when thecopolymers are used alone in corresponding equivalent total amounts ofthe copolymers. In various embodiments of the invention, the copolymerscan be used as a mixture of two chinolinium-modified copolymers, amixture of an alkyl-modified copolymer with a chinolinium-modifiedcopolymer, a mixture of an imidazolium-modified copolymer and achinolinium-modified copolymer, and a mixture of an alkyl-modifiedcopolymer and an imidazolium-modified copolymer.

The dewatering and desalting agents and formulations of the inventioncan include a mixture of two copolymers in a ratio of about 1:1. Themixtures of the copolymers can be a mixture of a copolymer of Formula 1and a copolymer of Formula 2, a mixture of a copolymer of Formula 1 andat least one copolymer of Formula 3 or Formula 4, a mixture of acopolymer of Formula 2 and at least one copolymer of Formula 3 orFormula 4, a mixture of a copolymer of Formula 2 and a copolymer ofFormula 5, and a mixture of a copolymer of Formula 1 and a copolymer ofFormula 5.

BRIEF DESCRIPTION OF THE DRAWINGS

The figures of this application are graphic showing the results of theassessment of the dewatering and desalting activity of crude oil by theaddition of the block copolymers α,ω-bifunctionalized with tertiaryamines (aliphatic and aromatics), individually and in a formulationcontaining the copolymers. In these examples, the crude oil hasgravities in the range of 14-23° API. In addition, the results of acommercial formulation so-called IMP-RHS-5 are included.

FIG. 1 is a graph showing the demulsifying activity of (23H-26H)triblock copolymers α,ω-bifunctionalized with tertiary amines, on CM1crude oil at 80° C. and 600 ppm.

FIG. 2 is a graph showing the demulsifying activity of (27H-29H)triblock copolymers α,ω-bifunctionalized with tertiary amines, on CM1crude oil at 80° C. and 600 ppm.

FIG. 3 is a graph showing the demulsifying activity of (26H to 27H-29H)(300 ppm/300 ppm) formulation of triblock copolymers ofα,ω-bifunctionalized with tertiary amines on CM1 crude oil at 80° C.

FIG. 4 is a graph showing the demulsifying activity of compositions of(24H to 25H-29H) (300 ppm/300 ppm) triblock copolymers ofα,ω-bifunctionalized with tertiary amines on CM1 crude oil at 80° C.

FIG. 5 is a graph showing the demulsifying activity of compositions of(23H to 24H-29H) (300 ppm/300 ppm) triblock copolymers ofα,ω-bifunctionalized with tertiary amines on CM1 crude oil at 80° C.

FIG. 6 is a graph showing the demulsifying activity of compositions of(26H/28H) triblock copolymers of α,ω-bifunctionalized with tertiaryamines on crude oil CM1 at 80° C.

FIG. 7 is a graph showing the demulsifying activity of compositions of(26H/27H) triblock copolymers of α,ω-bifunctionalized with tertiaryamines on CM1 crude oil at 80° C.

FIG. 8 is a graph showing the demulsifying activity of compositions of(25H to 26H-29H) (300 ppm/300 ppm) triblock copolymers inα,ω-bifunctionalized with tertiary amines and IMP-RHS5 formulation at600 ppm on CM2 crude oil at 80° C.

FIG. 9 is a graph showing the demulsifying activity of compositions of(26H to 27H-29H) (300 ppm/300 ppm) triblock copolymers inα,ω-bifunctionalized with tertiary amines and IMP-RHS5 formulation at600 ppm on CM2 crude oil at 80° C.

FIG. 10 is a graph showing the demulsifying activity of compositions of(26H/27H) triblock copolymers based on α,ω-bifunctionalized withtertiary amines and the IMP-RHS5 commercial formulation on CM3 crude oilat 80° C.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to the synthesis of novel block copolymerswith low polydispersity like poly(ethylene oxide)-poly(propyleneoxide)-poly(ethylene oxide), using ethylene glycol as initiator, andwhere the copolymers are α,ω-bifunctionalized with tertiary amines(aliphatic and aromatic). The efficiency of the above copolymers isattributed to having a polydispersity of about 1.02 to 1.20, thebifunctionalization with tertiary amines (aliphatic and aromatic) andmolecular weights in the range of 1000 to 4000 Daltons, and preferably1200 to 2700 Daltons.

The experimental process development for synthesizing theabove-described compounds, consisted in the following three steps:

1. Synthesis ofpoly(oxyethylene)_(w)-poly(oxypropylene)_(y)-poly(oxyethylene)_(w) blockcopolymers. In one embodiment, the alkylene oxide has the formula Rdiscussed below.

2. Alkyl and aryl sulfonation of the terminal α,ω-hydroxyl groups of thepoly(oxyethylene)_(w)-poly(oxypropylene)_(y)-poly(oxyethylene)_(w) blockcopolymers.

3. Nucleophilic substitution of α,ω-alkyl and arylsulfonates ofpoly(oxyethylene)_(w)-poly(oxypropylene)_(y)-poly(oxyethylene)_(w) blockcopolymers with tertiary amines (aliphatics and aromatics).

One method of producing block copolymers ofpoly(oxyethylene)-poly(oxypropylene)-poly(oxyethylene) and derivativesthereof is disclosed in commonly owned U.S. 2010/0140141, which ishereby incorporated by references in its entirety.

The novel α,ω-bifunctionalized block copolymers with tertiary amines(aliphatics and aromatics), is shown in the equations (1) to (5):

where R is

and where:

R represents triblock copolymers with a molecular weight ranging between1000 and 4000 Daltons, ofpoly(oxyethylene)_(w)-poly(oxypropylene)_(y)-poly(oxyethylene)_(w). Thepoly(oxyethylene)_(w)-poly(oxypropylene)_(y)-poly(oxyethylene)_(w) asthe starting material is preferably obtained using ethyleneglycol as aninitiator.

w and y are numbers ranging between of 10 to 60, preferably between 15to 55, even more preferably between 15 and 50.

R₁, R₂ and R₃ are independently radicals selected from the groupconsisting of —CH₂(CH₂)_(A)B; —CEGJ; —CH₂CHLM; —CH₂(CH₂)_(Q)M;

where A is a number between 1 and 19, B is H.

EGJ are independently radicals represented by: H, methyl, ethyl,n-propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, n-butyl, phenyl,cyclohexyl, cyclopentyl.

L is a radical represented by methyl and ethyl and M is a hydroxylgroup, Q is a number between 1 and 5; T is represented by the EGJ groupsand NO₂, Cl, F, Br.

R₄ is independently a radical represented by —(CH₂)_(A)B; —OU;—CH(C₆H₅)₂; —C(C₆H₅)₃, where A is a number between 1 and 19, B is H; Uis independently a radical represented by methyl, ethyl, and benzyl.

R₅ is independently a radical represented by -2(methyl-phenyl),-(4-methyl-phenyl), -(4-phenyl-phenyl); R₆ is independently a radicalrepresented by -(4-methoxy-phenyl), -(4-piperazinyl), NO₂; R₇ isindependently a radical represented by Br, (phenyl-sulfanyl),(methyl-sulfanyl); R₈ is independently a radical represented by NO₂ andbromide: R₉ is independently a radical represented by Br; R₁₀ isindependently a radical represented by (-octyloxy-); R₁₁ isindependently a radical represented by Br; R₁₂ is independently aradical represented by -methyl, -(4-methyl-phenyl), -(2-methoxy-phenyl);R₁₃ is a radical represented by NO₂, -(4-methyl-phenyl),-(3-methyl-phenyl), -(2-methyl-phenyl), -(2-methoxy-phenyl),-(3-methoxy-phenyl); R₁₄ is a radical represented by -methyl,-(2-phenoxy-ethoxy), -(4-nitro-phenoxy), -(4-phenoxy-butoxy).

Z is independently a radical represented by methansulfonate,benzensulfonate and para-toluenesulfonate.

The preferred amines of the present invention for producing the blockcopolymers are: dibutylhexadecylamine, triisooctylamine, trioctylamine,2-ethyl-N,N-bis(2-ethylhexyl)-hexylamine, dimethyl-docosyl-amine,N,N-dimethyl-hexadecylamine, trihexylamine, 1-benzyl-1H-imidazole,1-methyl-1H-imidazole, 1-pentyl-1H-imidazole, 1-butyl-1H-imidazole,1-vinyl-1H-imidazole, 1-ethyl-1H-imidazole, 1-lauryl-1H-imidazol,1-cyano-1H-imidazol, 1-hexyl-1H-imidazole, 1-propyl-1H-imidazole,1-benzyloxy-1H-imidazole, 1-ethoxy-1H-imidazole, 1-methoxy-1H-imidazole,1-methoxymethyl-1H-imidazole, 1-benzhydryl-1H-imidazole,1-(diethoxymethyl)-1H-imidazole, 1-(triphenylmethyl)-1H-imidazole,1-(2-methyl-phenyl)-isoquinoline, 1-(4-methyl-phenyl)-isoquinoline,1-(4-phenyl-phenyl)-isoquinoline, 3-(4-methoxy-phenyl)-isoquinoline,3-(4-piperazinyl)-isoquinoline, 3-nitro-isoquinoline,4-bromo-isoquinoline, 4-phenyl-sulfanyl-isoquinoline,4-methyl-sulfanyl-isoquinoline, 5-nitro-isoquinoline,5-bromo-isoquinoline, 6-bromo-isoquinoline, 7-octyloxy-isoquinoline,5,8-dibromo-isoquinoline, quinoline, 8-(2-phenoxy-ethoxy)-quinoline,2,8-dimethyl-quinoline, 3-nitroquinoline, 3-(3-methyl-phenyl)-quinoline,3-(2-methyl-phenyl)-quinoline, 3-(4methoxy-phenyl)-quinoline,3-(3-methoxy-phenyl)-quinoline, 3-(2-methoxy-phenyl)-quinoline,2-(benzyloxy)-quinoline, 2-(4-methyl-phenyl)-quinoline,2-(2-methoxy-phenyl)-quinoline, 8-(4-nitro-phenoxy)-quinoline,8-(4-phenoxy-butoxy)-quinoline, 2,8-dimethyl-quinoline,3,4-dimethyl-pyridine, 4-(4-nitro-phenyl)-pyridine, pyridine,3-(4-bromo-phenyl)-pyridine, 3-(4-nitro-phenyl)-pyridine, and4-(cyclohexyl-methyl)-pyridine.

Examples of particularly preferred copolymers include:

α,ω-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-ammonium, wherethe aliphatic amines can be linear or branched, functionalized orunfunctionalized aliphatic groups,

α,ω-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-ammonium, wherethe aromatic amines are derivatives of 1H-alkyl-imidazole,1H-aryl-imidazole, 1H-alkyl-functionalized-imidazole and1H-aryl-functionalized-imidazole,

α,ω-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-isoquinolinium,where the aromatic amines are derivatives of isoquinoline that can befunctionalized or unfunctionalized,

α,ω-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-quinolinium, wherethe aromatic amines are derivatives of quinolone that can befunctionalized or unfunctionalized,

α,ω-di-aryl or alkyl sulfonates of PEO-PPO-PEO of bis-pyridinium, wherethe aromatic amines are derivatives of pyridine can be functionalized orunfunctionalized.

SYNTHESIS OF FUNCTIONALIZED BLOCK COPOLYMERS

The experimental procedure earlier mentioned was described widely inprevious applications U.S. 2010/0140141 and MX/2008/015156; the presentinvention is distinguished from previous processes because thenucleophilic substitution is carried out with tertiary amines (aliphaticand aromatic) according to the present invention.

The following is a detailed description of one embodiment of the presentinvention.

Nucleophilic substitution of the α,ω-alkyl and aryl sulfonates of theblock copolymers poly(ethylene oxide)-poly(propyleneoxide)-poly(ethylene oxide) with tertiary amines)

10 mmoles of the copolymer α,ω-dialkyl-sulfonate-ester orα,ω-diaryl-sulfonate-ester of poly(ethylene oxide)_(w)-poly(propyleneoxide)_(y)-poly(ethylene oxide)_(w). (Mn=2200-2500 g/mole, I=1.12) and50 mL of toluene were put in a bottom rounded flask with three necks,magnetic stirrer, condenser and addition funnel. Afterwards, 10.2 mmoleof the aliphatic or aromatic tertiary amine dissolved in toluene wereslowly added to the copolymer, keeping the temperature between 30 and35° C. and submitted to a reflux heating for 17 hours. After this time,the solvent was eliminated at reduced pressure.

Once the copolymers were obtained, they were submitted tocharacterization using the following instrumental methods:

1.—Spectrometer of Fourier transform infrared Brucker® tensor model 27,employing ATR method with OPUS® software.

2.—Spectrometer of nuclear magnetic resonance Varian® model BB at 200MHz to obtain ¹H and 50 MHz ¹³C spectra, employing deuterated chloroformand deuterated dimethylsulfoxide as solvents. The signal shifts aregiven in parts per million (δ) referred to the tetramethylsilane (TMS)as internal standard.3.—Size exclusion chromatograph (SEC) of Agilent® model 1100, furnishedwith PlegI column and using tetrahydrofurane (THF) as eluent, used todetermine the distribution of the copolymers molecular weights andpolydispersity(I).

TABLE NO. 1 Molecular mass number averages (Mn) and polydispersity index(I) of poly(ethylene oxide)_(w)-poly(propylene oxide)_(y)-poly(ethyleneoxide)_(w), (POE-POP-POE) copolymers prepared using potassium ethyleneglycolate as initiator. Copolymer Mn (g/mole) I Physical state A 40001.15 Solid B 4000 1.12 Viscous liquid C 2900 1.17 Viscous liquid D 27001.11 Viscous liquid E 2400 1.12 Viscous liquid F 1700 1.14 Viscousliquid G 1350 1.15 Viscous liquid Where: A, B, C, D, E, F, and G arepoly(ethylene oxide)_(w)-poly(propylene oxide)_(y)-poly(ethyleneoxide)_(w), (POE_(w)-POP_(y)-POE_(w)) copolymers, which exhibitdifferent molecular weight number averages and polydispersity index, sothey were labeled with letters A to G.

The spectroscopic characterization of some bifunctionalized copolymersis now depicted. These examples are illustrative but not limiting:

(IMP-CF23H) α,ω-di-para-toluensulfonate of poly(ethyleneoxide)_(w)-poly(propylene oxide)_(y)-poly(ethylene oxide)_(w) ofbis-tri-octyl-ammonium: viscous liquid; I.R. ν cm⁻¹: 2978, 2953, 2870,2790, 1595, 1459, 1383, 1354, 1174, 1100, 1069, 977, 825, 775, 752; ¹³CNMR (DMSO-d₆): 13.9, 17.1, 21.6, 21.2, 21.8, 25.7, 25.8, 42.7, 60.5,60.7, 63.2, 70.2, 70.5, 72.9, 73.5, 75.1, 75.4, 75.7, 127.9, 130.0,132.7, 145.1.

(IMP-CF24H) α,ω-di-benzensulfonate of poly(ethyleneoxide)_(w)-poly(propylene oxide)_(y)-poly(ethylene oxide)_(w) ofbis-tri-hexyl-ammonium: viscous liquid; I.R. ν cm⁻¹: 2975, 2948, 2865,2790, 1595, 1459, 1383, 1354, 1172, 1100, 1069, 975, 825, 775, 751; ¹³CNMR (DMSO-d₆): 14.0, 17.1, 22.5, 25.7, 27.0, 42.6, 60.6, 60.7, 63.2,70.2, 70.5, 72.9, 73.5, 75.1, 75.4, 75.7, 127.9, 129.41, 134.6, 135.1.

(IMP-CF25H) α,ω-di-benzensulfonate of poly(ethyleneoxide)_(w)-poly(propylene oxide)_(y)-poly(ethylene oxide)_(w) ofbis-1H-methyl-imidazolium: viscous liquid; I.R. ν cm⁻¹: 3049, 2930,2858, 1571, 1468, 1385, 1170, 1102, 1018, 895, 767, 655 ¹³C NMR(DMSO-d₆): 17.2, 36.2, 42.8, 60.6, 60.8, 63.1, 70.2, 70.4, 72.8, 75.1,75.5, 75.7, 121.9, 123.7, 129.4, 134.5, 135.2, 137.6.

(IMP-CF26H) α,ω-di-benzensulfonate of poly(ethyleneoxide)_(w)-poly(propylene oxide)_(y)-poly(ethylene oxide)_(w) ofbis-1H-butyl-imidazolium: viscous liquid; I.R. ν cm⁻¹: 3052, 2945, 2863,1565, 1465, 1380, 1165, 1102, 1018, 896, 765, 655; ¹³C NMR (DMSO-d₆):15.5, 17.2, 22.3, 31.0, 36.2, 45.1, 60.6, 60.8, 63.1, 70.2, 70.4, 72.8,75.1, 75.5, 75.7, 122.1, 123.6, 127.4, 129.2, 133.5, 136.2, 137.6.

(IMP-CF27H) α,ω-di-benzensulfonate of poly(ethyleneoxide)_(w)-poly(propylene oxide)_(y)-poly(ethylene oxide)_(w) ofbis-isochinolinium: viscous liquid; I.R. ν cm⁻¹: 3023, 2971, 2965, 2856,1641, 1607; 1583, 1526, 1482, 1470, 1390, 1177, 1173, 1165, 1112, 1105,983, 946, 819, 759; ¹³C NMR (DMSO-d₆): 17.1, 46.1, 60.4, 60.7, 64.1,70.3, 70.4, 72.9, 75.2, 75.3, 75.7, 126.4, 127.1, 127.8, 128.0, 129.4,131.2, 134.0, 134.5, 135.2, 137.0, 137.3, 150.2.

(IMP-CF28H) α,ω-di-benzensulfonate of poly(ethyleneoxide)_(w)-poly(propylene oxide)_(y)-poly(ethylene oxide)_(w) ofbis-chinolinium: viscous liquid; I.R. ν cm⁻¹: 3056, 3024, 2950, 2921,2865, 2728, 1624, 1598, 1590, 1525, 1466, 1407, 1383, 1276, 1209, 1175,1165, 1153, 1134, 1105, 989, 875, 801, 777, 771; ¹³C NMR (DMSO-d₆):17.2, 45.8, 60.4, 60.7, 64.1, 70.3, 70.4, 72.9, 75.2, 75.3, 75.7, 118.9,122.2, 127.8, 129.3, 129.7, 129.80, 130.7, 135.1, 135.2, 137.3, 147.2,149.5.

(IMP-CF29H) α,ω-di-benzensulfonate of poly(ethyleneoxide)_(w)-poly(propylene oxide)_(y)-poly(ethylene oxide)_(w) ofbis-pyridinium: viscous liquid; I.R. ν cm⁻¹:3068, 3010, 2970, 2960,2850, 1633, 1620, 1598, 1482, 1436, 1388, 1275, 1217, 1174, 1162, 1108,980, 872, 750; ¹³C NMR (DMSO-d₆): 17.1, 45.9, 60.4, 60.9, 64.0, 70.3,70.4, 72.9, 75.2, 75.2, 75.7, 127.4, 128.0, 129.6, 134.1, 135.2, 142.1,146.0.

A second feature of the present invention is directed to the preparationof dewatering and desalting agents and formulations based onpoly(ethylene oxide)_(w)-poly(propylene oxide)_(y)-poly(ethyleneoxide)_(w) block copolymers α,ω-bifunctionalized with tertiary amines(aliphatics and aromatics), using solvents with boiling point between 35to 200° C., preferably dichloromethane, chloroform, benzene, toluene,xylenes, turbosine, naphtha, individually or mixtures thereof. Preparedsolutions include amounts ranging from 100 ppm (0.01 wt. %) to 50000 ppm(5 wt. %) of the copolymers.

A third feature of the present invention is relates to the applicationof the prepared solutions in methods for dehydrating and desaltingagents of crude oils with gravities ranging between 14-23° API, byadding small volumes of dissolution or formulation and avoiding thesolvent effect influenced on the emulsion breaking.

Individual and Prepared Composition Evaluation from the Block Copolymerα,ω-Bifunctionalized with Tertiary Amines Aliphatic and Aromatics, asDehydrating and Desalting Agents on Crude Oils with API GravitiesRanging Between 14-23° API.

Different concentrated dissolutions and formulations were prepared foreach of the bifunctionalized copolymers from 5 to 40% by weight,employing disolvents with boiling point is ranging from 35 to 200° C.,preferably dichloromethane, chloroform, benzene, toluene, xylenes,turbosine, naphtha, individually or in mixtures thereof, and addingsmall volumes of the dissolution to avoid the solvent effect influencedon the emulsion breaking. Block copolymers bifunctionalized wereprepared in concentrations of 100 to 50000 ppm.

Three crude oils identified as CM1, CM2 and CM3 used in this evaluationwere characterized as is shown following:

TABLE NO. 2 Physicochemistry characterization of crude oils Test CM1 CM2CM3 API gravity 14.9 19.3 22.2 Sal content (lbs/1000ls) 10870 248 7050Paraffin (wt. %) 4.4 3.6 3.7 Distilled water (vol. %) 26.0 20 13.0Water/sediment (vol. %) 24.7 19 12.6 Runoff Temperature (° C.) −18 −30−24 Kinematic viscosity (mm²/s) 2302 343 1161.4 Heptane Insoluble (wt.%) 10.2 10.8 7.7 Saturated (wt. %) 11.8 20.7 13.9 Aromatics (wt. %) 31.726.8 39.7 Resins (wt. %) 45.7 43.4 39.1 Asphaltenes (wt. %) 10.8 9.1 7.3MW Cryoscopy (g/mole) 511 370 374 CII 0.296 0.424 0.274

Evaluation procedure was described in detail in U.S. 2010/0140141 andU.S. 2012/026312, which are hereby incorporated by reference in theirentirety. Then and by way of demonstration that involves no limitation,it shows the graphic results, in the concentration intervals appliedranging from 100 ppm to 1200 ppm.

From FIGS. 1 and 2 (application concentration 600 ppm on CM1 crude oil),it observes that IMP-CF26H, IMP-CF27H, and IMP-CF28H bifunctionalizedcopolymers are able to break up the emulsion with high yields giving 84%(390 minutes), 81% (210 minutes), and 77% (390 minutes), respectively;whereas the formulation IMP-RHS5 (25 minutes) breaks up very quicklythen stays stable in efficiency 58%.

Continuing with CM1 crude oil, shown in FIG. 3 that IMP-CF 26H/IMP-CF27H (300 ppm/300 ppm) composition reached 100% of yield on the emulsionbreaking at 360 minutes of treatment, therefore, there is a synergybetween these two copolymers, because individually (600 ppm) onlyreached 84% and 81% of yield on the emulsion breaking.

In FIG. 4, it is observed that the best composition is IMP-CF 24H/IMP-CF28H (89%, 300 minutes) and IMP-CF24H/IMP-CF27H with 85% of efficiency at300 minutes of treatment; whereas in FIG. 5 is observed thatIMP-CF23H/IMP-CF28H and IMP-CF23H/IMP-CF26H compositions are able tobreak up the emulsion with 85% of yield at 300 minutes, all theseformulations were applied on CM1 crude oil in concentration of 300ppm/300 ppm, and to overcome the efficiency of the novel evaluatedcopolymers individually, again it observes that there exists a synergywith this novel kind of copolymers.

In FIG. 6 (CM1 crude oil), in the left side, it is represented theemulsion breaking efficiency using the IMP-CF26H/IMP-CF28H compositionin different concentrations, the best of all is 250 ppm/250 ppm, giving96% at 5 hours, showing that exists major synergism at lowconcentration, thus the formulation of 300 ppm/300 ppm breaks up theemulsion at 390 minutes with an efficiency of 78%.

On the right side of the same FIG. 7, the efficiency of theIMP-CF26H/IMP-CF27H composition, at 300 ppm/300 ppm, shows 100% ofrupture, whereas the concentrations of 250/250 and 200/200 ppm/ppmreached 96% of the emulsion breaking in the same time. The range ofconcentrations applied in both compositions ranging from 100 ppm/100 ppmto 300 ppm/300 ppm.

TABLE NO. 3 Efficiency in the crude desalting CM1 with differentcompositions. Dehy- De- drated Salt salted Composition ppm/ppm % Time¹Remains² % IMP-CF26H/IMP-CF 27H 300/300 100 360 2600 76.0IMP-CF26H/IMP-CF27H 250/250 96 300 2850 73.8 IMP-CF26H/IMP-CF27H 200/20096 300 2475 77.2 IMP-CF26H/IMP-CF28H 250/250 96 300 1010 90.7¹(minutes), ²(lbs/1000 barrels)

Desalted data shown in Table No. 3 indicate that the highest percentage(907%) was achieved with the IMP-CF26H/IMP-CF28H (250 ppm/250 ppm)composition, other compositions have similar values.

FIG. 8 shows the results of the formulations prepared from theIMP-CF25H/IMP-CF29H and IMP-CF25H/IMP28H copolymers which breaks the100% of the water-in-oil emulsion, in 150 minutes and 320 minutes,respectively when they are applied over CM2 crude oil; whereas FIG. 9clearly shows that the best compositions were IMP-CF26H/IMP-CF29H andIMP-CF26H/IMP-CF28H, both formulations achieved 100% of rupture at 150minutes and 260 minutes respectively.

FIG. 10 (Crude oil CM3) shows that the best composition is composed byIMP-CF26H/IMP-CF27H 300 ppm/300 ppm compared to IMP-CF26H/IMP-CF27H,which reach the emulsion breaking at 120 minutes with an efficiency of92%.

TABLE NO. 4 Efficiency of desalting process in the CM3crude oil withdifferent compositions Dehy- De- drated Salt salted Composition ppm/ppm% Time¹ Remains² % IMP-CF26H/IMP-CF27H 300/300 92 120 2475 65.0IMP-CF26H/IMP-CF27H 250/250 86 100 2600 63.1 ¹(minutes), ²(lbs/1000barrels)

The results of Table No. 4 indicate that the higher dehydrationpercentage the greater desalting percentage.

Thus, the compositions prepared from the block copolymersbifunctionalized with tertiary amines of this invention together withthe block copolymers bifunctionalized with secondary amines are moreeffective in the dehydrated and desalted of Mexican crude oils than theIMP-RHS-5 commercial formulation.

What is claimed is:
 1. A method of dewatering and desalting crude oil, comprising: mixing a dewatering and desalting agent and a crude oil having a specific gravity of about 14 to 23° API at a concentration of at least 100 ppm, wherein said dewatering and desalting agent comprises at least one compound selected from the group consisting of Formula 1 and Formula 5;

where R is

and R represents a copolymer with a molecular weight in the range from 1000 to 4000 Daltons, w and v are independently a whole number consistent with the molecular weight, R₁, R₂ and R₃ radicals are independently selected from the group consisting of —CH₂(CH₂)_(A)B; —CEGJ; —CH₂CHLM; —CH₂(CH₂)_(Q)M;

where A is a number between 1 and 9, B is H, E, G and J are a radical independently selected from the group consisting of:—H, methyl, ethyl, n-propyl, iso-propyl, sec-butyl, iso-butyl, tert-butyl, n-butyl, phenyl, cyclohexyl, and cyclopentyl, L is a radical represented by methyl or ethyl, and M is a hydroxyl group, O is a number between 1 and 5, T is represented by groups E, G and J, NO₂, Cl, F and Br; and Z is a radical independently selected from the group consisting of methanesulfonate, benzenesulfonate and para-toluenesulfonate.
 2. The method of claim 1, wherein said copolymer is a mixture in a solvent having a boiling point of about 35° C. to about 200° C., said method comprising adding said mixture to the crude oil.
 3. The method of claim 2, wherein said solvent is selected from the group consisting of dichloromethane, chloroform, benzene, toluene, xylene, turbosine, naphtha and mixtures thereof, and where said mixture is added in an amount of 0.01% to 5% by weight.
 4. The method of claim 1, wherein said dewatering and desalting agent comprises a mixture of two of said copolymers in a ratio of about 1:1 to said crude oil.
 5. The method of claim 1, wherein said dewatering and desalting agent comprises a mixture of a copolymer of Formula 1 and at least one copolymer of Formula
 5. 